Process for preparing N-alkyl ammonium acetonitrile compounds

ABSTRACT

A process is provided for the preparation of a compound having the structure of Formula I                    
     The process includes reacting a heterocyclic amine with a monoaldehyde or a dialdehyde in a pH range of from about 8 to 14 and then quaternizing the so-reacted heterocyclic amine with an alkylating agent at a pH of not less than about 2. The use of pH control substantially prevents formation of an undesirable protonated reaction intermediate.

This is a continuation of application Ser. No. 08/905,511, filed Aug. 4,1997, now abandoned; which was a continuation application of Ser. No.08/758,542, filed Nov. 29, 1996, now abandoned; which was acontinuation-in-part application of Ser. No. 08/475,292, filed Jun. 7,1995, now U.S. Pat. No. 5,739,327, issued Apr. 14, 1998.

FIELD OF THE INVENTION

The present invention generally relates to N-alkyl ammonium acetonitrilecompounds useful in applications such as bleaching and cleaning andparticularly relates to a process for the preparation of such compounds.

This application is a continuation in part of Ser. No. 08/475,292, filedJun. 7, 1995, entitled “N-ALKYL AMMONIUM ACETONITRILE BLEACHACTIVATORS,” inventors Arbogast et al., of common assignment herewith.

BACKGROUND OF THE INVENTION

Peroxy compounds are effective bleaching agents, and compositionsincluding mono- or di-peroxyacid compounds are useful for industrial orhome laundering operations. For example, U.S. Pat. No. 3,996,152, issuedDec. 7, 1976, inventors Edwards et al., discloses bleaching compositionsincluding peroxygen compounds such as diperazelaic acid anddiperisophthalic acid.

Peroxyacids (also known as “peracids”) have typically been prepared bythe reaction of carboxylic acids with hydrogen peroxide in the presenceof sulfuric acid. For example, U.S. Pat. No. 4,337,213, inventorsMarynowski et al., issued Jun. 29, 1982, discloses a method for makingdiperoxyacids in which a high solids throughput may be achieved.

However, granular bleaching products containing peroxyacid compoundstend to lose bleaching activity during storage, due to decomposition ofthe peroxyacid. The relative instability of peroxyacid can present aproblem of storage stability for compositions consisting of or includingperoxyacids.

One approach to the problem of reduced bleaching activity of peroxyacidcompositions has been to include activators of hydrogen peroxide or anactive oxygen source. U.S. Pat. No. 4,283,301, inventor Diehl, issuedAug. 11, 1981, discloses bleaching compositions including peroxygenbleaching compounds, such as sodium perborate monohydrate or sodiumperborate tetrahydrate, and activator compounds such as isopropenylhexanoate and hexanoyl malonic acid diethyl ester.

Other examples of activators include tetraacetyl ethylenediamine (TAED),nonanoyloxy benzene-sulfonate (NOBS), and nonanoylglycolate phenolsulfonate (NOGPS). NOBS and TAED are disclosed, for example, in U.S.Pat. No. 4,417,934, Chung et al., and NOGPS is disclosed, for example,in U.S. Pat. No. 4,778,618, Fong et al., the disclosures of which areincorporated herein by reference.

Thus, U.S. Pat. No. 4,778,618, Fong et al., issued Oct. 18, 1988provides novel bleaching compositions comprising peracid precursors withthe general structure

wherein R is C₁₋₂₀ linear or branched alkyl, alkylethoxylated,cycloalkyl, aryl, substituted aryl; R′ and R″ are independently H, C₁₋₂₀alkyl, aryl, C₁₋₂₀ alkylaryl, substituted aryl, and N⁺R₃ ^(α), whereinR^(α) is C₁₋₃₀ alkyl; and where L is a leaving group which can bedisplaced in a peroxygen bleaching solution by peroxide anion. U.S. Pat.No. 5,182,045, issued Jan. 26, 1993, and U.S. Pat. No. 5,391,812, issuedFeb. 21, 1995, inventors Rowland et al. are similar, but arepolyglycolates of the Fong et al. monoglycolate precursors, oractivators.

U.S. Pat. No. 4,915,863, issued Apr. 10, 1990, inventors Aoyagi et al.,discloses compounds said to be peracid precursors that have nitrilemoieties. U.S. Pat. No. 5,236,616, issued Aug. 17, 1993, inventors Oakeset al., discloses compounds said to be cationic peroxyacid precursorsthat have nitrile moieties. These nitrile containing activators do notcontain a leaving group, such as the Fong et al. leaving groups, butinstead include a quaternary ammonium group suggested as activating thenitrile and said, upon reaction or perhydrolysis in the presence ofhydrogen peroxide, to generate a peroxy imidic acid as bleachingspecies. The Aoyagi et al. activators include an aromatic ring, whichtends to cause fabric yellowing.

German patent application P4431212.1, published Mar. 7, 1996 describesproduction of quaternized glycinonitriles in the form of stable aqueoussolutions.

New peroxygen activators that provide excellent bleaching and that canbe formulated for liquid or solid compositions remain desirable forapplications such as laundry and household bleaching and cleaning.

SUMMARY OF THE INVENTION

In one aspect of the present invention, nitrites are provided insubstantially solid form having the structure of Formula I

wherein A is a saturated ring formed by five atoms in addition to the N₁atom, the five saturated ring atoms being four carbon atoms and aheteroatom, the substituent R₁ bound to the N₁ atom of the Formula Istructure including either (a) a C₁₋₂₄ alkyl or alkoxylated alkyl wherethe alkoxy is C₂₋₄, (b) a C₄₋₂₄ cycloalkyl, (c) a C₇₋₂₄ alkaryl, (d) arepeating or nonrepeating alkoxy or alkoxylated alcohol, where thealkoxy unit is C₂₋₂₄, or (e) —CR₂R₃C≡N where R₂ and R₃ are each H, aC₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or a repeating or nonrepeatingalkoxyl or alkoxylated alcohol where the alkoxy unit is C₂₋₄.

The Formula I compounds have a quaternary nitrogen atom (N₁), requiringthe presence of at least one counterion (Y) to be associated therewith,which is illustrated in Formula I as “Y^(⊖),” but as understood can bemonovalent, or multivalent. Y includes counterions, or organic andinorganic anions, such as chloride, bromide, nitrate, alkyl sulfate,bisulfate, sulfate, tosylate, and mesylate. Especially preferred aremethyl sulfate, sulfate, bisulfate, tosylate, and mixtures thereof. Zwill be in the range of 0 to 10. These compounds, or salts, areparticularly well suited to granule bleaching and cleaning compositions.

The nitriles with the Formula I structure are particularly useful whenformulated as compositions that include a source of active oxygen, andthese compositions provide excellent bleaching in alkaline solutions.

Preferred embodiments include lower alkyls substituted at the N₁, e.g.N-methyl morpholinium acetonitrile, N-ethyl morpholinium acetonitrile,N-butyl morpholinium acetonitrile, which are illustrated by Formula II(with “n” preferably being 0 to 24 and where “Y” is one of the abovedescribed counterions).

A particularly preferred embodiment is an N-methyl morpholiniumacetonitrile salt where “n” of Formula II is 0. In the preferred processfor preparing the Formula I or Formula II compounds, decomposition of aprocess intermediate is substantially avoided so as to reduce amounts ofundesired free hydrogen cyanide, preferably to below the analyticaldetection limit. In a preferred embodiment of the process, a compoundwith the structure of Formula II is prepared to be substantially free ofhydrogen cyanide by reacting morpholine with a monoaldehyde or adialdehyde and hydrogen cyanide or an alkali metal cyanide in an aqueousmedium (Step A) and then with an alkylating agent (Step B), whereby StepA is carried out in a pH range of from 8 to 14 and Step B is carried outat a pH of not less than about 2. Most preferably, Step B is carried outat a pH of not less than about 3.

Compositions including these nitriles are useful, for example, inlaundry products, such as bleaching additives, detergents, detergentboosters, detergents with bleach, bleaches, bleaching aids, stainremovers, and spot treatment products such as stain removers, prewashand presoak laundry aids. Among the advantages derived from suchcompositions are improved cleaning, stain removal, spot removal,whitening, and brightening of treated articles.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

Application Ser. No. 08/475,291, filed Jun. 7, 1995, entitled “N-AlkylAmmonium Acetonitrile Bleach Activators,” describes nitrites, typicallyquaternized, for which a preferred embodiment was N-methyl ammoniumacetonitrile methylsulfate, to which this application relates. There areseveral aspects of the present invention.

One aspect is wherein novel quaternized nitriles are provided havingcertain counterions which result in substantially reduced hygroscopicity(with respect to amorphous N-methyl ammonium acetonitrile methylsulfate,or MMAMS). Another aspect is wherein novel nitrites are provided asgranules by being carried, coated, or admixed with a suitableparticulate material. These granules have improved stability and/orreduced hygroscopic characteristics with respect to amorphous MMAMS. Yetanother aspect of the invention is for an improved process of makingnovel quaternized nitrites so as to have reduced amounts of undesiredby-product.

All these inventive aspects have as a common element certain novelnitrites with the structure generally illustrated by Formula I. The N₁atom of the Formula I compound is part of a saturated ring, illustratedby “A” in Formula I.

This saturated ring of which N₁ is a part has a plurality of atoms. Thesaturated ring illustrated by ring “A” in Formula I preferably has atleast one hetero atom in the saturated ring in addition to the N₁, morepreferably wherein the ring includes an oxygen atom, a sulfur atom, orone or two additional nitrogen atoms.

The at least one nitrogen in the saturated ring (N₁) shown in Formula Iis N-acetonitrile substituted and also quaternized. Without being boundby theory, the electron withdrawing nature of the quaternary nitrogenmay be increased by being part of a saturated, heterocyclic ring and mayalso function to improve the hydrophilic character of the oxidant.

A substituent R₁ will be bonded to the N₁ atom of the Formula Istructure and additionally a nitrile moiety (—CR₂R₃C≡N) is bonded to theN₁ atom, where R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl, oralkaryl, or a repeating or nonrepeating alkoxyl or alkoxylated alcoholwhere the alkoxy unit is C₂₋₄. The R₁ substituent may be a C₁₋₂₄ alkylor alkoxylated alkyl where the alkoxy is C₂₋₄, C₄₋₂₄ cycloalkyl, a C₇₋₂₄alkaryl, a repeating or nonrepeating alkoxy or alkoxylated alcohol,where the alkoxy unit is C₂₋₄, and illustrative such groups are, forexample,

where j=1 to 24. The R₁ substituent may also be another —CR₂R₃C≡N, andagain R₂ and R₃ are each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or arepeating or nonrepeating alkoxyl or alkoxylated alcohol where thealkoxy unit is C₂₋₄, and illustrative such groups are:

where j=1 to 24.

Particularly preferred, saturated rings forming the cyclic configurationA of Formula I contain six atoms including the N₁ atom, but the numberof atoms forming the cyclic configuration can range from 3 to 9. Whentwo heteroatoms are present with the cyclic configuration A of FormulaI, then a three member ring is unusual; but, for the cyclicconfiguration B of Formula III shown below, where there may only be N₁as the sole heteroatom, then three membered rings are very likely.

As already noted, the particularly preferred saturated ring of which N₁is a part has five atoms in addition to N₁, with at least one heteroatom being in the saturated ring in addition to the N₁, preferablywherein the heteroatom of the ring is an oxygen atom or a sulfur atom,most preferably where the heteroatom is oxygen.

Particularly preferred activator embodiments are illustrated by FormulaII (where “Y” and “Z” will be hereinafter described, and “n” is 0 to24).

Derivatives of the Formulas I and II nitriles include peroxyimidicintermediates that are believed formed from the nitrites in the presenceof an active oxygen source. So formed, peroxyimidic derivativestypically would be short-lived intermediates formed in situ when thenitrites of the invention interact with a source of hydrogen peroxideand where the reactive nitrile moiety forms a peroxyimidic acid.However, such peroxyimidic derivatives may also be prepared in situ byanalogy to syntheses known in the art.

Counterions

Since the novel nitrile compounds are normally quaternized, they willinclude at least one counterion (designated as “Y”). Suitablecounterions are monovalent or multivalent and include tosylates, loweralkyl tosylate (e.g. methyl tosylate and ethyl tosylate), and mesylates.Further, in the earlier noted copending application Ser. No. 08/475,292,filed Jun. 7, 1995, N-alkyl ammonium acetonitrile compounds aredisclosed as typically including a wide variety of counterions such aschloride, bromide, nitrate, alkyl sulfate, and the like, and wherein apreferred embodiment was described therein as N-methyl ammoniumacetonitrile methylsulfate.

When one chooses the granule aspect of this invention, then such a widevariety of counterions remain available in choosing which counterion maybe desired, including methylsulfate as counterion. This is because mostof the granule embodiments protect stability of the nitrile (forexample, against humidity during storage). However, the novel nitrilecompounds need not be in granule form in order to be suitable for manyapplications and to provide compounds stabilized against moisturepick-up.

One particularly preferred embodiment herein is where the counterionsare either sulfate, bisulfate, or mixtures thereof. Such a sulfate orbisulfate salt (or mixtures thereof) may be produced from heated andacidified N-methyl morpholinium acetonitrile methylsulfate, or MMAMS(wherein the counterion before the conversion to bisulfate or sulfate ismethylsulfate). These two particularly preferred salts are illustratedby Formula IIIA and IIIB. A third particularly preferred salt, N-methylmorpholinium acetonitrile tosylate (“MMATS”), is illustrated by FormulaIIIC.

The MMABS, MMAS, and MMATS embodiments are particularly useful where onewishes a substantially solid composition to have reduced hygroscopicitywith respect to MMAMS. Although the MMABS, MMAS, and MMATS embodimentsmay also be in granule form, they need not be, and are usable incrystalline or amorphous forms.

The sulfate and bisulfate counterions are in equilibrium with oneanother in solution, and the predominant species is dependent on thesolution pH. Above pH 2, the sulfate group predominates, while below pH2 the bisulfate form predominates. Thus, the particular form desired maybe obtained by controlling the solution pH, although a mixture isobtained at an intermediate pH.

However, the particularly preferred embodiment is where granules areprovided in which the nitrile salt is bisulfate that has beencrystallized, the crystals redissolved, and the solution (thus havingimpurities removed) is granulated.

Nitrile Water Content

The novel nitriles may exist either as anhydrous salts (essentially freeof water) or as stable hydrates having discrete amounts of water ofhydration. Thus, in Formulas I and II, Z is in the range of 0 to 10,preferably 0 to 6, and most preferably 0 to 1. This “Z” may be viewed asan average number of moles of hydration. Because there may be mixturesof the Formulas I and II compounds with integer numbers of moles ofhydration, the actual value for Z may be a non-integer value. The valuefor Z may be reduced when one converts a crystalline or amorphous formof novel nitrile into a granulated form.

Physical Form of Nitriles

Amorphous forms of the Formulas I and II nitrites may be obtained byrapid evaporation or precipitation from solutions (such as in spraydrying, column drying, and the like). Alternatively, crystalline saltsmay be obtained by crystallization or careful evaporation, whichcrystalline forms tend to be less hygroscopic than amorphous forms. Thisreduced hygroscopicity of the crystalline salts is believed, withoutbeing bound to theory, due to the tight packing of the molecules withinthe crystal that prevent bulk water penetration and the reduced totalsurface area of a crystalline solid compared to an amorphous form of thesame solid. Granule embodiments may also be prepared from the nitritesin either the crystallized or amorphous forms.

Surprising Advantages of the Manufacturing Process

Because the preparation of nitrites can generate intermediates (believedto be a protonated morpholine reaction intermediate when morpholine isused in preparing the Formula II compounds) that can decompose toundesirable free hydrogen cyanide, a process for producing the nitritesin which free hydrogen cyanide is virtually no longer detectable ishighly desirable. Practice of the inventive process is successful inreducing the values for free hydrogen cyanide from less than about 5 ppmto 0 (wherein 0 signifies as being below the analytical detectionlimit).

Bleaching and Cleaning Compositions

Bleaching and cleaning compositions of the invention include the FormulaI nitrile salts as activator, together with a source of active oxygen.

The peroxide or active oxygen source for compositions of the inventionmay be selected from the alkaline earth metal salts of percarbonate,perborate, persilicate and hydrogen peroxide adducts and hydrogenperoxide. Most preferred are sodium percarbonate, sodium perborate mono-and tetrahydrate, and hydrogen peroxide. Other peroxygen sources may bepossible, such as monopersulfates and monoperphosphates, or theirequivalent aqueous forms, such as monopersulfuric acid, known in thetrade as Caro's acid or Caroate, a product of BASF AG, Germany.

The range of peroxide to activator is preferably determined as a molarratio of peroxide to activator. Thus, the range of peroxide to eachactivator is a molar ratio of from about 0.1:1 to 100:1, more preferablyabout 1:1 to 10:1 and most preferably about 2:1 to 8:1. This peracidactivator/peroxide composition should provide about 0.5 to 100 ppm A.O.,more preferably about 1 to 50 ppm peracid A.O. (active oxygen), and mostpreferably about 1 to 20 ppm peracid A.O., in aqueous media for typicallaundry applications. Formulations intended for hard surface cleaningwill more typically have peracid activator/peroxide providing from about0.5 to 1,000 ppm A.O., more preferably about 1 to 500 ppm peracid A.O.,and most preferably about 1 to 200 ppm peracid A.O.

Compositions of the invention have been found to provide superiorbleaching (cleaning and stain removal) benefits on common laundrystains.

Granular Embodiments and Delivery Systems

The substantially solid salt activators can be directly used in acrystalline or amorphous form, for example by incorporating into a solidmatrix in solid detergent bleaches. As will be hereinafter more fullydescribed, preparation of the novel nitrites in bisulfate or sulfateform will typically be by converting from another counterion (e.g.methylsulfate). The conversion may be complete or partial. Thus, aFormula I or II salt composition may include from about 1 wt. % to about99 wt. % of another compound related to the Formula I compound, butdiffering therefrom in counterion. The degree of conversion to bisulfateor sulfate will be directly related to the amount of hygroscopicityreduction of such a salt composition.

Whether converted to bisulfate or sulfate or not, incorporation of thenovel nitrile salts into dry, or granulated, formulations can beachieved through several different embodiments. Granulated formulationshold several advantages over liquid formations, such as for example,reduced shipping costs. Other advantages are an increased stability ofthe nitrile activator against moisture, alkalinity (e.g. carbonate),against premature activation, and reduction in possible dye damage.

Typically, the precursor composition before granulation is of sprayableconsistency, that is to say, in the form of a melt, suspension, orsolution. One suitable process for granulation may be performed in afluid bed or rotatory drum agglomerator, such as is described by U.S.Ser. No. 08/554,672, filed Nov. 8, 1995, entitled “Agglomerated ColorantSpeckle Exhibiting Reduced Colorant Spotting,” incorporated herein byreference.

In the granular embodiments the nitrile salts can be carried by, coatedwith or admixed with a solid particulate, such as an inert, porousmaterial. These granules can further have a coating that is sufficientto delay dissolution in aqueous solution. For example, appropriate suchcoatings include surfactants, waxes, polymers, or melts thereof, anddusting or flow agents such as silicas and silicates. The coatings canencapsulate the nitrile-containing core.

Granules preferably have an average particle size of from about 3 nm toabout 2 mm. For example, activators of the invention can be dispersedonto a solid or granulated carrier such as silica gel, silicic acid,silicate, aluminum oxide, kaolin, aluminum silicate, mixtures or othercarriers such as clay, zeolite, organic polymers including starch andion exchange material. Additional solids useful for carriers includealkali metal and alkaline earth salts of carbonate, bicarbonate,sesquicarbonate, phosphate, chloride, sulfate, bisulfate, and borate.

A high internal surface area of the carrier materials is preferred forsuch a granular embodiment. The total surface area preferably lies inthe range from 10 to 500 m²/g or, especially, 100 to 460 m²/g or,especially, 250 to 450 m²/g.

Although most conventional types of chemically inert, porous materialscan be used as carrier materials, silicic acids, silicates, precipitatedsilicas, aluminum oxides, various varieties of clays or aluminumsilicates or mixtures thereof are preferred.

Silica gels (silica gels, silicic acid gels) are colloidal, formed orunformed silicic acids of elastic to solid consistency with a loose tocompact pore structure and a high adsorption capacity. Silica gelsurfaces usually exhibit acidic properties. Silica gel is usuallymanufactured from water-glass by reaction with mineral acids.Precipitated silicas are powders obtained by coagulation of silicaparticles from an aqueous medium under the influence of coagulants.

Among the silicic acids, thermally generated silicic acids, i.e. highlydispersed “pyrogenic” SiO₂ qualities (e.g. the Aerosils® or Cab-o-Sils®)that are usually prepared by flame hydrolysis of SiCl₄ can be usedespecially advantageously in addition to silicic acids that are obtainedin accordance with the wet process. In a specially preferred form ofembodiment of the present invention, use is made of silicic acid with anaverage (agglomerate) particle size of 100 nm or 30 mm or, especially,100 μm to 1.5 mm and a SiO₂ content of 95 to 100% by weight or,preferably, 98 to 100% by weight. In addition, precipitated silicone,such as SIPERNAT® silica material can be used advantageously.

Aluminum oxides occur in nature in, for example, the form ofargillaceous earth or as corundum. In this regard, the aluminum oxide ispresent in the α-modification. Industrially, α-Al₂O₃ is obtained frombauxite using the Bayer process. Suitable “active” aluminum oxides witha high specific surface area are prepared in the form of adsorbents, viaprecipitation procedures, from aluminum salt solutions or via thecalcination of α-aluminum hydroxide.

Clays are naturally occurring crystalline and amorphous hydratedsilicates of aluminum, iron, magnesium, calcium, potassium, and sodium.These clays may also contain amounts of aluminum oxides and silica.Useful clays may include kaolins, serpentines, talcs, pyrophyllites,attapulgites, sepiolites, montmorillonites, and bauxitic clays. Theseclays may undergo various processes before use. For example, clays maybe air-floated, water-washed, calcined, delaminated, acid activated, ortreated with dispersants.

A preferred process for providing an aluminum silicate carrier particleis disclosed by Ser. No. 08/554,672, noted above, which process can alsobe used for providing a carrier for a pigment or other colorant.Aluminum silicates are compounds with different proportions of Al₂O₃ andSiO₂. Aluminum silicate minerals in which Al occupies lattice positionsin the crystal lattice in the place of Si are the aluminosilicates (e.g.the various varieties of ultramarine, zeolite, and feldspar). Freshlyprecipitated aluminum silicates are finely dispersed and have a largesurface area and a high adsorption capacity. Among usefulaluminosilicates are synthetic zeolites commonly used as detergentbuilders.

The ratio of nitrile salt and carrier materials in a solid composition.in accordance with the invention can vary within certain limits,depending on the method of manufacturing the solid composition and theproperties of the carrier, and the final end use. A preferred ratio is10 to 95 parts by weight of the nitrile to 5 to 90 parts by weight ofthe carrier, especially 10 to 70 parts of weight of the nitrile to 10 to70 parts by weight of the carrier. A ratio of 50 to 90 parts by weightof Formula I to 10 to 50 parts by weight of carrier is especiallypreferred where the desire is to maximize the concentration of activeFormula I. A ratio of 50 to 10 parts by weight of Formula I to 10 to 90parts by weight of carrier is especially preferred where the desire isto disperse the active Formula I, for instance to reduce localizedbleaching. The indicated parts by weight are based on the anhydroussolid. For example, granules of the invention may include one surfactantor a mixture of surfactants so as to constitute an amount preferably ofabout 0.5 to about 50 parts by weight.

Surfactants of Delivery Systems

As earlier mentioned, compositions of the invention frequently desirablycontain varying amounts of surfactants, which may act both as a cleaningactive agent as well as also to help disperse sparingly solublematerials in liquid phase when the compositions are put to use.

Surfactants with which the activators and active oxygen compositions maybe combined or admixed include linear ethoxylated alcohols, such asthose sold by Shell Chemical Company under the brand name Neodol. Othersuitable nonionic surfactants can include other linear ethoxylatedalcohols with an average length of 6 to 16 carbon atoms and averagingabout 2 to 20 moles of ethylene oxide per mole of alcohol; linear andbranched, primary and secondary ethoxylated, propoxylated alcohols withan average length of about 6 to 16 carbon atoms and averaging 0-10 molesof ethylene oxide and about 1 to 10 moles of propylene oxide per mole ofalcohol; linear and branched alkylphenoxy (polyethoxy) alcohols,otherwise known as ethoxylated alkylphenols, with an average chainlength of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethyleneoxide per mole of alcohol; and mixtures thereof.

Further suitable nonionic surfactants may include polyoxyethylenecarboxylic acid esters, fatty acid glycerol esters, fatty acid andethoxylated fatty acid alkanolamides, certain block copolymers ofpropylene oxide and ethylene oxide, and block polymers or propyleneoxide and ethylene oxide with propoxylated ethylene diamine. Alsoincluded are such semi-polar nonionic surfactants like amine oxides,phosphine oxides, sulfoxides and their ethoxylated derivatives.

Anionic surfactants may also be suitable. Examples of such anionicsurfactants may include the ammonium, substituted ammonium (e.g.,mono-di-, and triethanolammonium), alkali metal and alkaline earth metalsalts of C₆-C₂₀ fatty acids and rosin acids, linear and branched alkylbenzene sulfonates, alkylethoxylated ether sulfates, alkylethoxylated orpropoxylated ether sulfates, alkyl sulfates, alkyl ether sulfates,alkane sulfonates, alpha olefin sulfonates, hydroxyalkane sulfonates,fatty acid monoglyceride sulfates, alkyl glyceryl ether sulfates, acylsarcosinates and acyl N-methyltaurides.

Suitable cationic surfactants may include the quaternary ammoniumcompounds in which typically one of the groups linked to the nitrogenatom is a C₁₂-C₁₈ alkyl group and the other three groups are shortchained alkyl groups which may bear inert substituents such as phenylgroups.

Suitable amphoteric and zwitterionic surfactants containing an anionicwater-solubilizing group, a cationic group or a hydrophobic organicgroup include amino carboxylic acids and their salts, amino dicarboxylicacids and their salts, alkyl-betaines, alkyl aminopropylbetaines,sulfobetaines, alkyl imidazolinium derivatives, certain quaternaryammonium compounds, certain quaternary phosphonium compounds and certaintertiary sulfonium compounds.

Other common detergent adjuncts may be added if a bleach or detergentbleach product is desired. Table 1 illustrates dry bleaching compositionembodiments incorporating the Formula I salts.

TABLE 1 COMPONENT COMPONENT RANGES (Wt. %) Surfactant: Linear alkylbenzene sulfonate (LAS) 0-15 Alkyl Sulfate (AS) 0-15 Alcohol ethoxysulfate (AEOS) 0-15 Alcohol ethoxylate (AE) 0-15 Builder: Sodiumcarbonate 20-70  Zeolite 0-50 Polyacrylate polymer 0-5  Sodium silicate0-8  Filler: Sodium chloride 0-30 Sodium sulfate 0-30 Water 0-5 Bleaching System: Sodium perborate monohydrate 4-40 MMA¹ activator 1-10Other: Enzyme(s)² 0-3  Brightener 0-2  Dye/Pigment as needed Perfume asneeded ¹Inventive nitrile, preferably MMAMS, MMAS, MMABS, or MMATS.²Examples include but are not limited to protease, amylase, lipase,cellulase (alone or in combinations)

Sources of Acid/Alkali

Compositions of the invention, when combined with a source of activeoxygen, preferably function for bleaching best at an alkaline pH, butare shelf stabilized best at an acidic pH, particularly a pH of from0-5, more preferably 0-2, most preferably 0-1. Thus, compositions of theinvention preferably include a source of protons as an “acid sink.” Thiscan be achieved, for example, by adding acid, preferably at levels fromabout 0-50 wt. % of final solid weight to liquid containing the nitritesprior to any further granulation processing (mixing or drying).Preferred acids include citric acid, sulfuric acid, succinic acid,hydrochloric acid, sulfurous acid, aryl sulfonic acids and alkyl arylsulfonic acids, as well as polyacrylic acid, maleic acid, nitric acid,and sulfamic acid. Most preferred are sulfuric acid and sulfurous acid.

When the composition is ready for use, it is especially advantageous tohave an amount of alkaline buffer present sufficient to maintain a pHgreater than about 8, more preferably in the range of about 8.5 to about10.5 for most effective bleaching, when the granules are dissolved ordispersed into an aqueous wash system. If used as a hard surfacecleaner, on the other hand, it may be useful to co-dispense the alkalinebuffer in a separate, preferably liquid, composition. These alkalinebuffers include, but are not limited to, alkali metal hydroxides(sodium, lithium, potassium), ammonium hydroxide, alkali metal andammonium carbonates, alkali metal and ammonium carbamates, alkali metaland ammonium polyacrylates, alkali metal and ammonium succinates, alkalimetal and ammonium maleates and additional conjugate bases of weakorganic acids, such as those mentioned hereinabove. Further, organicbases are included, such as, without limitation, ethanolamine,diethanolamine, triethanolamine, hydroxyamine, methylamine,dimethylamine, and trimethylamine.

Additional Functional/Aesthetic Adjuncts

Other adjuncts (useful in cleaning and laundering applications) areoptionally included in the inventive compositions. Dyes includeanthraquinone and similar blue dyes. Pigments may also be used, and canhave a bluing effect by depositing on fabrics washed with a detergentbleach containing UMB. Monastral colorants are also possible forinclusion. Brighteners or whiteners, such as stilbene, styrene andstyrylnaphthalene brighteners (fluorescent whitening agents), may beincluded. Fragrances used for aesthetic purposes are commerciallyavailable from Norda, International Flavors and Fragrances, andGivaudon. Stabilizers include hydrated salts, such as magnesium sulfate,and boric acid.

In some of the compositions herein, adjuvants include (and areespecially preferred) a chelating agent or sequestrant, and preferably anon-phosphate containing sesquesterant, and most preferably, anaminopolyphosphonate. These chelating agents assist in maintaining thesolution stability of the salt activators and active oxygen source inorder to achieve optimum performance. In this manner, they are acting tochelate heavy metal ions, which cause catalyzed decomposition of theactive oxygen source and of the (believed) in situ formed peroxyimidicacids, although this is a non-binding theory of their action and notlimiting.

The chelating agent is selected from a number of known agents which areeffective at chelating heavy metal ions. The chelating agent should beresistant to hydrolysis and rapid oxidation by oxidants. Preferably, itshould have an acid dissociation constant (pKa) of about 1-9, indicatingthat it dissociates at low pH's to enhance binding to metal cations.Acceptable amounts of the (optional) chelating agent range from 0-1,000,more preferably 5-500, most preferably 10-100 ppm chelating agent, inthe wash liquor.

The most preferred chelating agent is an aminopolyphosphonate, which iscommercially available under the trademark Dequest from MonsantoCompany. Examples thereof are Dequest 2000, 2041, and 2060. (See alsoBossu U.S. Pat. No. 4,473,507, column 12, line 63 through column 13,line 22, incorporated herein by reference.) A polyphosphonate, such asDequest 2010, is also suitable for use.

Other preferred non-phosphate containing chelating agents, such asethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA)may also be suitable for use. Still other new, preferred chelatingagents are new propylenediaminetetraacetates, such as Hampshire 1,3PDTA, from W. R. Grace, and Chel DTPA 100#F, from Ciba Geigy A. G.Mixtures of the foregoing may be suitable.

Additional desirable adjuncts are enzymes (although it may be preferredto also include an enzyme stabilizer). Proteases are one especiallypreferred class of enzymes. They are preferably selected from alkalineproteases. The term “alkaline,” refers to the pH at which the enzymes'activity is optimal. Alkaline proteases are available from a widevariety of sources, and are typically produced from variousmicroorganism (e.g., Bacillus subtilisis). Typical examples of alkalineproteases include Maxatase and Maxacal from International BioSynthetics,Alcalase, Savinase, and Esperase, all available from Novo Industri A/S.See also Stanislowski et al., U.S. Pat. No. 4,511,490, incorporatedherein by reference. Further suitable enzymes are amylases, which arecarbohydrate-hydrolyzing enzymes. It is also preferred to includemixtures of amylases and proteases. Suitable amylases include Rapidase,from Societe Rapidase, Milezyme from Miles Laboratory, and Maxamyl fromInternational BioSynthetics.

Still other suitable enzymes are cellulases, such as those described inTai, U.S. Pat. No. 4,479,881, Murata et al., U.S. Pat. No. 4,443,355,Barbesgaard et al., U.S. Pat. No. 4,435,307, and Ohya et al., U.S. Pat.No. 3,983,082, incorporated herein by reference.

Yet other suitable enzymes are lipases, such as those described inSilver, U.S. Pat. No. 3,950,277, and Thom et al., U.S. Pat. No.4,707,291, incorporated herein by reference.

The hydrolytic enzyme should be present in an amount of about 0.01-5%,more preferably about 0.01-3%, and most preferably about 0.1-2% byweight of the composition. Mixtures of any of the foregoing hydrolasesare desirable, especially protease/amylase blends.

Anti-redeposition agents, such as carboxy-methylcellulose, arepotentially desirable. Foam boosters, such as appropriate anionicsurfactants, may be appropriate for inclusion herein. Also, in the caseof excess foaming resulting from the use of certain surfactants,anti-foaming agents, such as alkylated polysiloxanes, e.g.dimethylpolysiloxane, would be desirable.

Preferred Granule Size, Density and Shape

Granule particle sizes can range from about 100 μm to about 1200 μm,more preferably 150-850 μm. Granule density will normally range fromabout 0.5 g/c³ to about 1.0 g/c³, more preferably 0.65 g/c³ to about0.80 g/c³. A wide variety of granule shapes may be used, includingspheres, hearts, moons, stars, clovers, cylindrical sections, and cubicsections.

Applications

Compositions of the invention are useful as or in laundry products, suchas bleaching additives, detergents, detergent boosters, detergents withbleach, bleaches, bleaching aids, and stain removers. Among theadvantages derived from compositions of the invention are improvedcleaning, stain removal, spot removal, whitening, and brightening oftreated articles.

Other product applications include household cleaning products, such ashard surface cleaners to be wetted with or dissolved in water prior touse. Exemplary surface cleaners are tile and grout cleaners, bathroom(floor, toilet, and counter) and kitchen (floor, sink, and counter)cleaners. Additionally, kitchen products such as dishwasher detergentswith bleach or bleach cleaning and scrubbing pads are contemplated.Among the benefits derived from use of the inventive compositions insuch applications are improved stain and spot removal and generalcleaning of the treated surfaces to remove food, rust, grime, mildew,mold, and other typical stains found on such surfaces.

Additionally, non-household product applications are contemplated wherean effective level of active oxygen generated in situ to treat water isuseful. Illustrative of such applications are pool and spa additives, aswell as cleaners to remove stains on outdoor concrete, stucco, siding,wood and plastic surfaces.

Preparation of the Nitriles

In general, N-quaternary acetonitrile compounds may be readily preparedfrom N-acetonitrile precursors by employing selected alkyl halides andusing well-known synthetic approaches, such as are described byMenschutkin, Z. Physik. Chem., 5, 589 (1890), and Z. Physik. Chem., 6,41 (1890); Abraham, Progr. Phys. Org. Chem., 11, 1 (1974); Arnett, J.Am. Chem. Soc., 102, 5892 (1980); German application DE 05 44 312 212.All these are incorporated by reference.

Compounds having the Formula I structure have a saturated ring formed bya plurality of atoms, broadly ranging from 3 to 9, although preferablycontaining 6 atoms including the N₁ atom. Preparation of these compoundswill most conveniently start with a compound already having the formedring. For example, a number of preparations of inventive nitriteshereinafter described will begin with morpholine (see, e.g., the FormulaII structure). An example of three membered rings is aziridine, e.g.,N-methylacetonitrile aziridinium; as an example of four membered ringsthere is azetidine, e.g., N-ethyl-acetonitrile azetidinium; as anexample of five membered rings there is pyrrolidine, e.g.,N-butylacetonitrile pyrrolidinium; as an example of six membered rings,in addition to morpholine, there is piperidine, e.g.,N-methylacetonitrile piperidinium; as an example of seven membered ringsthere is homopiperidinium; as an example of eight membered rings thereis tropane, e.g., N-methylacetonitrile-8-azabicyclo[3.2.1]octane; and,as an example of nine membered rings there is octahydroindole, e.g.,N-methylacetonitrile octahydroindolinium.

More particularly, in the preferred method of preparation a suitableamine is reacted with a monoaldehyde or a dialdehyde and with HCN or analkali metal cyanide in an aqueous medium (Step A) followed bysubsequent quaternization (Step B) with an alkylating agent. In Step A,the reaction is preferably either in the pH range from 8 through 14, andthe pH value is maintained at not less than 2 in Step B.

Thus, an amine with the formula

is reacted as Step A with a monoaldehyde or a dialdehyde R⁶—CHO orOHC—R⁵—CHO, whereby R⁵ is a chemical bond or a C₁ to C₆ alkylene bridgeor an oxyethylene bridge, and R⁶ stands for H or C₁ to C₂₀ alkyl, andwith hydrogen cyanide or an alkali metal cyanide in an aqueous medium.Step B is quaternization with an alkylating agent R¹—X in an aqueousmedium without isolating the intermediate product from Step A. Preferredalkylating agents are dimethylsulfate, diethyl sulfate, a methyl halide,an ethyl halide, dimethyl carbonate, diethyl carbonate, methyl tosylate,ethyl tosylate, methyl mesylate, ethyl mesylate, or a benzyl halide.

In Step A, cyanohydrins, e.g., formaldehyde cyanohydrin, can be formedas by-products from the aldehyde, that is used, and hydrogen cyanide.These cyanohydrins do not react further with the alkylating agent inStep B so that renewed breaking down of the cyanohydrins into aldehydeand hydrogen cyanide in the final product is possible.

Without the procedure in accordance with the invention, Step B usuallyproceeds in such a way that, as a result of hydrolysis of the addedalkylating agent the pH value of the reaction mixture drifts off fromthe alkaline or neutral region into the strongly acidic region withincreasing reaction time. The protonation of the amine nitrogen atom ofthe glycinonitrile, that has not yet been quaternized, sets in—incompetition with alkylation—starting from a certain pH value so that, atthe end of the addition of the alkylating agent, no further reaction ofthe glycinonitrile takes place. Non-quaternized glycinonitrile in thefinal product can also represent an undesired source of hydrogencyanide.

Step A generates especially good results if a pH range of 9 through 13or, especially, 10 through 12, is utilized. In this pH range, thecyanohydrin that is formed is present in an equilibrium with thealdehyde and the hydrogen cyanide so that the re-formed adducts canreact to completion with the amine to give glycinonitrile.

If one also uses an excess of amine that amounts to about 2 through 20mole % or, especially, about 3 through 10 mole % or, most particularlyof all, about 4 through 7 mole %, based on the quantity of the hydrogencyanide or alkali metal cyanide that is used, then one achieves evenmore extensive suppression of hydrogen cyanide and ancillary components,that liberate hydrogen cyanide, in the final product.

Step B generates especially good results if the pH values are notreduced below 2.5 and, especially, not below 3. An optimum pH range forthe quaternization of Step B is 2.5 through 5 or, especially, 3 through4.

Use is also made of an excess of alkylating agent that amounts to 10 to40 mole % or, especially, 15 to 25 mole % based on the quantity of aminethat is used in Step A, then one achieves still more extensivesuppression of the hydrogen cyanide and the subsidiary components, thatliberate hydrogen cyanide, in the final product.

Once the nitrites are prepared in quaternized form, formation of thepreferred bisulfate or sulfate form preferably is by heating an alkylsulfate form, in an acid aqueous solution. For example, a suitableelevated temperature is about 40° C. to about 150° C., more preferablyabout 70° C. to about 110° C. The acid aqueous solution may have a pH inthe range of about −1 to 6, more preferably from about 0 to 3, with theheating being for a period of about 1 to 50 hours.

Aspects of the invention will now be illustrated by the followingexamples. It will be understood that these examples are intended toillustrate, and not to limit, the invention.

EXAMPLE 1

527.2 g (6.05 moles) of morpholine were introduced into the reactionvessel and cooled to 10° C. Within a period of one hour, 600 g (6.0moles) of formaldehyde (30% by weight) were then metered in. Theaddition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25% by weight)started half an hour after the start of the addition of formaldehyde.The time of addition amounted to 1 hour. During the addition, thetemperature was allowed to rise to 35° C. and stirring then took placefor a further hour at 35° C. Cooling to 30° C. then took place and 927.8g (7.35 moles) of dimethylsulfate (DMS) were added within 2 hours at 30°C. During the DMS addition, the pH value fell into the acidic regionstarting from 8. At pH 3.5, the pH-regulated addition of aqueous causticsoda (25% by weight) was counter-controlled so that the pH remainedconstant at 3.5 during the remaining addition time and the followingpost-reaction time of 3 hour at 30° C. The mixture was then heated to50° C. and the pH value was allowed to fall in this connection. After 1hour at 50° C., the excess DMS was completely destroyed. The pH valuewas then 1.

Analytical results: HCN  0 ppm formaldehyde cyanohydrin 74 ppmmorpholinoacetonitrile 55 ppm (Molar ratio HCN:CH₂O:morpholine =1:1.01:1.02; molar ratio morpholine:dimethylsulfate = 1:1.21)

EXAMPLE 2

527.2 g (6.05 moles) of morpholine were introduced into the reactionvessel and cooled to 10° C. 6.6 g of aqueous caustic soda (20% byweight) were added in order to raise the pH value. Within a period ofone hour, 600 g (6.0 moles) of formaldehyde (30% by-weight) were thenmetered in. The addition of 161.6 g (5.4 moles) of hydrogen cyanide(99.25% by weight) started half an hour after the start of the additionof formaldehyde. The time of addition amounted to 1 hour. During theaddition, the temperature was allowed to rise to 35° C. and stirringthen took place for a further hour at 35° C. The pH value amounted to11.4 at the end of this part of the synthesis. The pH was then adjustedto 8-8.2 with sulfuric acid. Cooling to 30° C. then took place and 932.4g (7.4 moles) of dimethylsulfate (DMS) were added within 2 hours at 30°C. During the DMS addition, the pH value fell into the acidic regionstarting from 8. At pH 3.5, the pH-regulated addition of aqueous causticsoda (25% by weight) was counter-controlled so that the pH remainedconstant at 3.5 during the remaining addition time and the followingpost-reaction time of 3 hour at 30° C. The mixture was then heated to50° C. and the pH value was allowed to fall in this connection. After 1hour at 50° C., the excess DMS was completely destroyed. The pH valuewas then 1.

Analytical results: HCN  0 ppm formaldehyde cyanohydrin 10 ppmmorpholinoacetonitrile 20 ppm (Molar ratio HCN:CH₂O:morpholine =1:1.01:1.02; molar ratio morpholine:dimethylsulfate = 1:1.22)

EXAMPLE 3

537.2 g (6.17 moles) of morpholine were introduced into the reactionvessel and cooled to 10° C. 6.7 g of aqueous caustic soda (20% byweight) were added in order to raise the pH value. Within a period ofone hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were thenmetered in. The addition of 161.6 g (5.94 moles) of hydrogen cyanide(99.25% by weight) started half an hour after the start of the additionof formaldehyde. The time of addition amounted to 1 hour. During theaddition, the temperature was allowed to rise to 35° C. and stirringthen took place for a further hour at 35° C. The pH value amounted to11.8 at the end of this part of the synthesis. The pH was then adjustedto 8-8.2 with sulfuric acid. Cooling to 30° C. then took place and 940 g(7.46 moles) of dimethylsulfate (DMS) were added at 30° C. within 2hours. During the DMS addition, the pH value fell into the acidic regionstarting from 8. At pH 3.5, the pH-regulated addition of aqueous causticsoda (25% by weight) was counter-controlled so that the pH remainedconstant at 3.5 during the remaining addition time and the followingpost-reaction time of 3 hour at 30° C. The addition of caustic soda tookplace with good mixing (stirring conditions of 800 revolutions/minute).The mixture was then heated to 50° C. and the pH value was allowed tofall in this connection. After 1 hour at 50° C., the excess DMS wascompletely destroyed. The pH value was then 1.

Analytical results: HCN  0 ppm formaldehyde cyanohydrin  0 ppmmorpholinoacetonitrile 20 ppm N-methylmorpholinium 58.0% by wt.acetonitrile methylsulfate N-methylmorpholinium  3.0% by wt. acetamidemethylsulfate (Molar ratio HCN:CH₂O:morpholine = 1:1.01:1.04; molarratio morpholine:dimethylsulfate = 1:1.21)

Example 4 illustrates another aspect of the invention, which is thepreparation of substantially solid bisulfate salts, such as to prepareMMABS.

EXAMPLE 4

The methylsulfate liquid, such as in any of Examples 1-3, was acidifiedto a pH of 0.1-1 followed by heating the resulting liquid under a slightvacuum (700-1000 mbar) in a vented container at temperatures of 90-110°C. for 3-5 hours.

The resulting bisulfate converted liquid may then be crystallized andpurified for recovery of crystalline nitrile salt, may be dried directlyonto a support/carrier to produce an amorphous salt, or may beredissolved after crystallization and then prepared in granule form. Onepreferred approach to promote the crystallization or precipitation maybe via addition of a “seed crystal,” which serves as a growth locationfor crystal formation. This seed crystal can be, but is not limited to,precipitated or fumed silica, or a sample of the bisulfate crystal saltitself. Another preferred approach is to allow the salt solution toprecipitate out by reducing the crystal solubility via cooling overtime.

EXAMPLE 5

96 kg of MMAMS liquid (48.5% active) were acidified with 6.7 kg ofsulfuric acid (50%) at 20° C. and subsequently heated to 110° C. for 4½hours after which the solution was cooled to 30° C. over an 18 hourperiod. The resulting slurry was then washed with water and filtrated toyield the resulting bisulfate crystal (61.7 kg)

When one wishes to prepare the nitrile salts in granule form, such canbe by use of various methods known to the art, such as fluid bed,agglomerating, spray coating, or melt mixing approaches, preferably atlevels of about 5-40 wt. % of the starting particulate weight. Thesegranules may have the nitrile salts carried on solid particulate or mayhave the nitrile salt coated by or admixed with solid particulate.

Conditions for coating preferably are whereby the temperature duringcoating is less than about 50° C. while the coating material is sprayedas a melt or dispersion onto the salt surface thereby coating orencapsulating the salt core. Example 6 illustrates different forms ofthe salt core and a variety of preferred coating materials. Anticipatedcoating materials include film-forming polymers, fatty acids, soaps, andother solid surfactants having a melting point above 40° C.

Nitrile Salt Core Preferred Coatings Materials Purified crystal saltPLURONIC 6800¹ Amorphous compacted salt PLURONIC 10500¹ Amorphousagglomerated salt PLURIOL E 6000¹ Amorphous acidified salt SOKALAN CP5¹LUWAX V¹ Polyvinyl alcohol Palmitic acid Paraffin Calcium AlginatePOLIGEN WE3¹ DIOFAN 193D¹ ¹Commercially available from BASF AG, Germany.

Particularly preferred coating materials are PLURIOL E6000 and LUWAX V.(PLURONIC is a trademark for a series ofpoly(oxyethylene-co-oxypropylene) block copolymers.)

EXAMPLE 7

Preparation of a Solid MMAMS/silicic Acid/surfactant Composition Using aStirring Process

3.4 kg of a highly dispersed silicic acid with a total surface area ofapproximately 450 m²/g and an average particle size of approximately 8mm (SIPERNAT® 50 S from the Degussa firm) and, additionally, 2.3 kg of atallow-based fatty alcohol that had been reacted with 25 mol of ethyleneoxide (Lutensol® AT 25 from the BASF firm) were stirred into 24.3 kg ofa 70% by weight aqueous solution of N-methylmorpholinium acetonitrilemethylsulfate (MMAMS). The liquid mixture was concentrated byevaporation in a paddle-type vacuum dryer at approximately 10 mbar and awall temperature of approximately 80° C. until a solid was formed thatwas capable of flowing (residual water content <1% by weight). Aftercooling, 20 kg of the solid composition were removed. The powder wascompacted by means of a conventional compactor to give flakes and theflakes were then broken up in a conventional sieve granulator and sievedto give a usable fraction of 400 to 1200 mm average size.

EXAMPLE 8

Manufacture of a Solid MMAMS/silicic Acid/surfactant Composition byMeans of a Spray Process

24.3 kg of a 70% by weight MMAMS solution were sprayed onto 31.6 kg ofthe highly dispersed silicic acid that was described in Example 7. Thecrumbly mixture was dried in a paddle-type vacuum dryer at approximately10 mbar and a wall temperature of approximately 80° C. until a finesolid was formed that was capable of flowing (residual water content <1%by weight). The product was then agglomerated in a mixture with a meltof 2.3 kg of the surfactant that was designated in Example 7. Finalprocessing to give a usable fraction of 400 to 1200 mm was carried outanalogously to Example 7.

EXAMPLE 9

Effect of Carrier Materials and Surfactants on the HygroscopicCharacteristics or, as the Case May be, the Flow Characteristics ofMMAMS

In order to ascertain the effect of ancillary substances on thehygroscopic characteristics or, as the case may be, the flowcharacteristics of MMAMS, three different samples were prepared in thepaddle-type dryer and were then stored in a desiccator at roomtemperature and a relative atmospheric humidity of 76%.

Sample 1: 2100 g MMAMS (solid) Sample 2: 3100 g MMAMS (solid)  400 gSIPERNAT 50 S Sample 3: 3100 g MMAMS (solid)  400 g SIPERNAT 50 S  233 gLutensol AT 25

All the samples were prepared from a 70% by weight aqueous MMAMSsolution analogously to Example 7 and were dried at 80° C. and 10 mbarin a paddle-type vacuum dryer with a volume of 5 liters until no morecondensate was generated.

In the case of Examples 8 and 9, one obtained a powder-type solid, thatwas capable of flowing after drying, with water contents of 0.74% byweight or 0.45% by weight, respectively; the MMAMS without the ancillarysubstances (sample 1) led to a wax-like, crumbly solid with a watercontent of 0.63% by weight.

These solids were then ground to the same average particle size and werestored in the desiccator. The results are presented in the followingTable 2.

It is clearly seen that solid MMAMS is obtained in a high concentrationand is stable on storage over a long period of time at a relativeatmospheric humidity of 76% only as a result of the addition of thedesignated ancillary substances.

TABLE 2 Storage time 0 hr 17 hrs 41 hrs 113 hrs Water Content % Sample 10.63 5.23 9.23 9.8 Ability to Flow Sample 1 capable baked on partiallypartially of detached detached flowing Water Content % Sample 2 0.745.04 9.04 11.44 Ability to Flow Sample 2 capable capable small slightlyof of clumps baked on flowing flowing Water Content % Sample 3 0.45 3.656.15 8.55 Ability to Flow Sample 3 capable capable capable capable of ofof of flowing flowing flowing flowing

EXAMPLE 10

Effect of Carrier Materials on the Storage Stability and Dye DamageCharacteristics

Samples of MMAMS on various carriers were prepared and put in ableaching composition to determine any benefit in storage stability ordye damage.

Storage Stability

The MMA methylsulfate has greater storage stability on an inert support,such as zeolite or clay. The presence of an acid sink, such as HLAS(alkylbenzenesulfonic acid), also enhances stability.

The MMA methylsulfate aqueous solution (3.6 g of 45%) was added to 38.5q of sodium carbonate containing 5.0 g of sodium perborate monohydrateand the solid dried. This was compared to first adding the MMAmethylsulfate to 6 parts of zeolite 4A (Valfour 100 from PQ Corp.) andthen adding to the sodium carbonate/perborate mixture. The MMAmethylsulfate could also be mixed with 6 parts of clay (AttapulgiteL96117 from Oil-Dry Corp.) and then added to the sodiumcarbonate/perborate mixture. The MMA methylsulfate was also mixed with 2parts of the same clay.

The results below in Table 3 show the surprisingly enhanced stabilitywhen the MMA methylsulfate is incorporated into the inventive supports.

TABLE 3 % MMA Active MMA substrate in after 1 wk StorageCarbonate/Perborate at 80° F/80% RH MMAMS  0% MMAMS/Zeolite = 1/6  98%MMAMS/HLAS/Zeolite = 1/2/6 100% MMAMS/Clay = 1/6 100% MMAMS/Clay = 1/2100%

Dye Damage Testing

The amount of MMAMS representing 5% of the base (sodiumcarbonate/perborate mixture) was placed on a diagnostic fabric (Brown100% cotton dyed with Fast Orange RD, Direct Brown 5R and Rapideger RedLD). The MMAMS was covered with the base and then 10 ml of deionizedwater was applied. After 10 minutes, the fabric was rinsed and allowedto dry. The dye damage was visually evaluated on a 0 to 10 scale, where0 represents no visible damage. The same samples as prepared above forthe stability testing were used. The results again show the benefit ofadding MMAMS to an inert support, with or without an acidic co-agent.

Nitrile Substrate Dye Damage Aqueous MMA methylsulfate 10  MMAMS/Zeolite= 1/6 3 MMAMS/HLAS/Zeolite = 1/2/6 1 MMAMS/Clay = 1/6 1

It is to be understood that while the invention has been described abovein conjunction with preferred specific embodiments, the description andexamples are intended to illustrate and not limit the scope of theinvention, which is defined by the scope of the appended claims.

It is claimed:
 1. A process for the preparation of a compound having thestructure of Formula I

wherein A is a saturated ring formed by a plurality of atoms in additionto the N₁ atom, the saturated ring atoms including at least one carbonatom and at least one heteroatom in addition to the N₁ atom, the saidheteroatom selected from the group consisting of O, S, and N atoms, thesubstituent R₁ bound to the N₁ atom of the Formula I structure is (a) aC₁₋₂₄ alkyl or alkoxylated alkyl where the alkoxy is C₂₋₄, (b) a C₄₋₂₄cycloalkyl, (c) a C₇₋₂₄ alkaryl, (d) a repeating or nonrepeating alkoxyor alkoxylated alcohol, where the alkoxy unit is C₂₋₄, or (e)—CR_(2′)R_(3′)C≡N where R_(2′) and R_(3′) are each H, a C₁₋₂₄ alkyl,cycloalkyl, or alkaryl, or a repeating or nonrepeating alkoxyl oralkoxylated alcohol where the alkoxy unit is C₂₋₄, the R₂ and R₃substituents being each H, a C₁₋₂₄ alkyl, cycloalkyl, or alkaryl, or arepeating or nonrepeating alkoxyl or alkoxylated alcohol where thealkoxy unit is C₂₋₄, Z is a value in the range of 0 to 10, and wherein Yis counterion, comprising the steps of: reacting a heterocyclic amine

 with (1) a monoaldehyde R⁶—CHO or a dialdehyde OHC—R⁵—CHO whereby R⁵ isa chemical bond or a C₁ to C₆ alkylene bridge and R⁶ stands for H or C₁to C₂₀ alkyl, and (2) hydrogen cyanide or an alkali metal cyanide in anaqueous medium (Step A) wherein the carrying out of Step A includesusing an excess of the amine that amounts to about 2 mole % to about 20mole % based on the quantity of hydrogen cyanide or alkali metalcyanide; and, quaternizing the so reacted heterocyclic amine with analkylating agent R¹—X (Step B), whereby Step A is carried out in a pHrange of from 8 to 14 and Step B is carried out at a pH of not less thanabout
 2. 2. The process as in claim 1 wherein A of Formula I is asaturated ring formed by four carbon atoms and one oxygen atom inaddition to the N₁ atom.
 3. The process as in claim 1 wherein carryingout Step B at a pH of not less than about 2 includes using an excess ofthe alkylating agent that amounts to about 10 mole % to about 40 mole %based on the quantity of the heterocyclic amine.
 4. The process as inclaim 1, 2, or 3 whereby the alkylating agent is dimethylsulfate,diethyl sulfate, a methyl halide, an ethyl halide, dimethyl carbonate,diethyl carbonate, methyl tosylate, ethyl tosylate, methyl mesylate,ethyl mesylate, or a benzyl halide.
 5. The process as in claim 4 wherebythe alkylating agent is dimethylsulfate.
 6. The process as in claim 5further comprising converting the methylsulfate counterion to bisulfateor sulfate.
 7. The process for preparing a compound with the structureof Formula II substantially free of hydrogen cyanide

wherein n is 0 to 24 and Y is counterion, comprising the steps of:reacting morpholine with (1) a monoaldehyde R⁶—CHO or a dialdehydeOHC—R⁵—CHO whereby R⁵ is a chemical bond or a C₁ to C₆ alkylene bridgeor oxyethylene bridge and R⁶ stands for H or C₁ to C₂₀ alkyl, and (2)hydrogen cyanide or an alkali metal cyanide in an aqueous medium (StepA) at a pH range from 8 to 14 using an excess of the amine that amountsto about 2 mole % to about 20 mole % based on the quantity of hydrogencyanide or alkali metal cyanide; and, quaternizing the so reactedmorpholine with an alkylating agent R¹—X, wherein R¹ is C₁-C₂₄ alkyl(Step B) is carried out at a pH effectively controlled to substantiallyprevent formation of a protonated morpholine reaction intermediate. 8.The process as in claim 7 wherein the pH is maintained during Step B atnot less than about
 2. 9. The process as in claim 8 whereby thealkylating agent is dimethylsulfate.